Ortho-hydroxy azo dye



Patented Oct; 22, 1940 r l UNITED, STATES I PAT NiE FiwCE 'halt, Germany,v assi'gnors' to General Aniline 2 I Film-Qorporation, a corporation of Delaware stalemate.- Application Jt1ys, 1'939,semm 282,690. In'Germany July '7, 1938 j GCIaims; (01.260-197) The present; invention relates to alprocess for suspension is run into a solution of 28.5 parts of manufacturing azo I dyes: and to the: products; thus l-methy1-4-chloro-5 hydroxynaphthalene- 1' -sulobtainable. .g fonic acid and 25 parts of sodium carbonate in It is known from U1 S. Patents Nos. 1,419,501 about 500 parts of water to which ice has been and 1,431,655 that valuable bluedyes capable of added. After coupling is complete the dye is being chromed are obtained by coupling halogen worked up in the usual manner. After drying it derivatives of the 2-hydroxy-diazo-benzene with constitutes a dark powder of good solubility a 8-halogeno 1 hydroxynaphthalene-5-sulfonic which dyes Wool navy-blue tints when applied by acid. When exposed to artificial light the tint of the after-chroming process.

0 these dyes, as described in said specifications, Example 2.24.7 parts of 3;4.5.6-tetrachloro- 10 generally changes only to a small extent. 2-amino-1-hydroxybenzene are introduced at 20' According to the present invention dyes capato 25 C. into 180 parts of sulfuric acid of 66 B; ble of being chromed are obtained the'dyeings of 7.5 parts of sodium nitrite are then added at 20 which have in the artificial light practically the C to 25 C. The mixture is heated for'one hour same tint if, instead of the 8-halogeno-1-hyat 50 C. and then cooled with ice. It is filtered 15 droxynaphthalene-5-sulfonic acid, thel-methylwith' suction and the residue on the filter is 4ch1oro-5-hydroxynaphthalene-1'-sulfonic acid washed witha small quantity of water; This is used as azo component. residue is-suspended with 200 parts of water for The 1-methyl-4-chloro-5-hydroxynaphthalenethe purpose of coupling and the suspension 0bl-sulfonic acid mentioned as azo component is tained is added to a solution of 28.5 parts of 1- 20 obtainable by treating 4-ch1oro-5-nitro-1-naphmethyl-.4 -chloro-5-hydr0xynaphthalene-1'-sulthornethyl chloride with sodium sulfite to form fonic acid and 8.2 parts of sodium bicarbonate in the l-methyl 4 chloro-5-nitronaphthalene-1- 1 250 parts of water with an addition of ice.- After sulfonic acid by reducing the nitro group and by coupling is complete 8 parts of sodium carbonate heating the amino acid thus formed with sulfuric are added; the dye'is then worked up in the usual 25 acid under pressure. The 4-chloro-5-nitro-1- manner. After drying it constitutes a dark pownaphthomethyl chloride mentioned above can be der which dissolves in water while assuming a' produced by chlorinating 1'-chloro-1-methyl-5- blue coloration; when applied to wool'by the onenitronaphthalene in the presence of an antimony fbath chroming process it yields a greenish, clear halide and dissolved in a trichlorinated hydronavy-blue.

carbon. For these specific processes for manu- Instead of the polych1or0-2-aminophenols facturing the said compounds we have filed sepnamed in the examples there may also be used, arate applications. I for instance, 4-chlor'0 2 amino-l-hydroxyben- The dyes obtained by the procedure which is. zene, 4.6 dichloro- 2 amino-l-hydroxybenzene,

the subject matter of the present invention show, 3.4.6 trichloro-5-bromo-2-amino-l-hydroxyben- 5 when appliedto wool by the one-bath chroming zene, 4.6 dichloro 3.5-dibromo-2-amino l-hyprocess or by an after-chroming process, a dis- 5 droxybenzene.

placement of the shade to the green side so that What we claim is: pure navy-blue dyein'gs are obtained which can- 1. The azo dyes which correspond to the gen- 40 not be produced with the known dyes. The eral formula 4 l 40 other properties of the dyeings such as fastness 0H 01 v to light, to washing, and to wet-processing are r A very good. a x

The following examples illustrate the invention, the parts being by weight: 7 X X 45 Example 1.-21.3 parts of 3.4.6-trichloro-2- amino-l-hydroxybenzene are suspended with 100 X C'HLSOaH parts of water, 30 parts of hydrochloric acid of 12 B are added and the whole is diazotized by in which X is a member of the group consisting of hydrogen, chlorine and bromine, at least one 50 means of 6.9 parts of sodium nitrite. The diazo of the Xs being one of the said halogens, said dyes dyeing wool in the presence of a chromium mordant or when combined with an after-chroming process pure navy-blue tints of excellent fastness to light and washing which are not altered in artificial light.

2. The azo dye which corresponds to the general formula 1 o1 01 oHlsolH said dye dyeing wool in the presence of a chromium mordant or when combined with an after-' chroming process pure navy-blue tints of excellent fastness to light and washing which are not altered in artificial light.-

3. The azo dye which corresponds to the general formula on on 01 N: t

I C] I CH2.SOaH

said dye dyeing wool in the presence of a chromium mordant or when combined with an afterchroming process pure navy-blue tints of excellent fastness to light and washing which are not altered in artificial light,

4. The process which comprises ,diazotizing an amine of the generalformula X NH:

1- hydroxy 2 amino-3.4.5.6-tetrachlorobenzene and coupling the diazo compound with'l-methyl- 4-chloro-5-hydroxynaphthalene1'-su1fonic acid.

OTTO HOFFMANN. HANS LANGE. 

